Size-dependent viscoelasticity in hybrid colloidal gels based on spherical soft nanoparticles and two-dimensional nanosilicates of varying size.

HYPOTHESIS: Hetero-aggregation of oppositely charged colloidal particles with controlled architectural and interactional asymmetry allows modifying gel nanostructure and properties. We hypothesize the relative size ratio between cationic nanospheres and varied-size anionic two-dimensional nanoclays will influence the gel formation mechanisms and resulting rheological performance. EXPERIMENTS: Hybrid colloidal gels formed via hetero-aggregation of cationic gelatin nanospheres (∼400 nm diameter) and five types of nanoclays with similar 1 nm thickness but different lateral sizes ranging from âˆ¼ 30 nm to âˆ¼ 3000 nm. Structure-property relationships were elucidated using a suite of techniques. Microscopy and scattering probed gel nanostructure and particle configuration. Rheology quantified linear and non-linear viscoelastic properties and yielding behavior. Birefringence and polarized imaging assessed size-dependent nanoclay alignment during shear flow. FINDINGS: Nanoclay size ratio relative to nanospheres affected the gelation process, network structure, elasticity, yielding, and shear response. Gels with comparably sized components showed maximum elasticity, while yield stress depended on nanoclay rotational mobility. Shear-induced nanoclay alignment was quantified by birefringence, which is more pronounced for larger nanoclay. Varying nanoclay size and interactions with nanospheres controlled dispersion, aggregation, and nematic ordering. These findings indicate that architectural and interactional asymmetry enables more control over gel properties through controlled assembly of anisotropic building blocks.

Engineering Nano/Microscale Chiral Self-Assembly in 3D Printed Constructs.

Helical hierarchy found in biomolecules like cellulose, chitin, and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms. This study advances the integration of helical/chiral assembly and 3D printing technology, providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries. We designed reactive chiral inks based on cellulose nanocrystal (CNC) suspensions and acrylamide monomers, enabling the chiral assembly at nano/microscale, beyond the resolution seen in printed materials. We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions. These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks, and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates, as well as their post-flow relaxation. Furthermore, we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath. These insights into the interplay between the chiral inks self-assembly dynamics, 3D printing flow kinematics and photo-polymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments, ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length, as well as random orientation of chiral domains. Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.

3D Printing-Assisted Self-Assembly to Bio-Inspired Bouligand Nanostructures.

Architected materials with nano/microscale orders can provide superior mechanical properties; however, reproducing such levels of ordering in complex structures has remained challenging. Inspired by Bouligand structures in nature, here, 3D printing of complex geometries with guided long-order radially twisted chiral hierarchy, using cellulose nanocrystals (CNC)-based inks is presented. Detailed rheological measurements, in situ flow analysis, polarized optical microscopy (POM), and director field analysis are employed to evaluate the chiral assembly over the printing process. It is demonstrated that shear flow forces inside the 3D printer's nozzle orient individual CNC particles forming a pseudo-nematic phase that relaxes to uniformly aligned concentric chiral nematic structures after the flow cessation. Acrylamide, a photo-curable monomer, is incorporated to arrest the concentric chiral arrangements within the printed filaments. The time series POM snapshots show that adding the photo-curable monomer at the optimized concentrations does not interfere with chiral self-assemblies and instead increases the chiral relaxation rate. Due to the liquid-like nature of the as-printed inks, optimized Carbopol microgels are used to support printed filaments before photo-polymerization. By paving the path towards developing bio-inspired materials with nanoscale hierarchies in larger-scale printed constructs, this biomimetic approach expands 3D printing materials beyond what has been realized so far.

Hybrid colloidal gels with tunable elasticity formed by charge-driven assembly between spherical soft nanoparticles and discotic nanosilicates.

Colloidal gels based on electrostatic interparticle attractions hold unexploited potential for tailoring their microstructure and properties. Here, we demonstrate that hetero-aggregation between oppositely charged particles with different geometries is a viable strategy for controlling their properties. Specifically, we studied hybrid colloidal gels prepared by the charge-driven assembly of oppositely charged spherical gelatin nanoparticles and two-dimensional (2D) nanosilicates. We show that the asymmetry between the building blocks and the resulting anisotropic interparticle interactions produces a variety of nanostructures and hybrid colloidal gels that exhibit high elasticity at low colloidal volume fractions. Tuning the competition between different attractive interactions in the system by varying the spatial charge heterogeneity on the 2D nanosheets, composition, and ionic strength was found to alter the mechanism of gel formation and their rheological properties. Remarkably, increasing the mass ratio of 2D nanosheets to spherical nanoparticles at a constant total mass fraction affords hybrid gels that exhibit an inverse relationship between elasticity and volume fraction. However, these hybrid gels are easily fluidized and exhibit rapid structural recovery once the stress is removed. These features allow for the engineering of versatile 3D-printable hybrid colloidal gels, whose structure and viscoelastic response are governed by parameters that have not been explored before.

Translocation Behaviors of Synthetic Polyelectrolytes through Alpha-Hemolysin (α-HL) and Mycobacterium smegmatis Porin A (MspA) Nanopores.

DNAs have been used as probes for nanopore sensing of noncharged biomacromolecules due to its negative phosphate backbone. Inspired by this, we explored the potential of diblock synthetic polyelectrolytes as more flexible and inexpensive nanopore sensing probes by investigating translocation behaviors of PEO-b-PSS and PEO-b-PVBTMA through commonly used alpha-hemolysin (α-HL) and Mycobacterium smegmatis porin A (MspA) nanopores. Translocation recordings in different configurations of pore orientation and testing voltage indicated efficient PEO-b-PSS translocations through α-HL and PEO-b-PVBTMA translocations through MspA. This work provides insight into synthetic polyelectrolyte-based probes to expand probe selection and flexibility for nanopore sensing.

Capillary Flow Characterizations of Chiral Nematic Cellulose Nanocrystal Suspensions.

Studying the flow-induced alignment of anisotropic liquid crystalline materials is of major importance in the 3D printing of advanced architectures. However, in situ characterization and quantitative measurements of local orientations during the 3D printing process are challenging. Here, we report a microfluidic strategy integrated with polarized optical microscopy (POM) to perform the in situ characterization of the alignment of cellulose nanocrystals (CNCs) under the shear-flow condition of the 3D printer's nozzle in the direct ink writing process. To quantify the alignment, we exploited birefringence measurements under white and monochromatic light. We show that the flow-induced birefringence patterns are significantly influenced by the initial structure of the aqueous CNC suspensions. Depending on the CNC concentration and sonication treatment, various structures can form in the CNC suspensions, such as isotropic, chiral nematic (cholesteric), and nematic (gel-like) structures. In the chiral nematic phase, in particular, the shear flow in the microfluidic capillary has a distinct effect on the alignment of the CNC particles. Our experimental results, complemented by hydrodynamic simulations, reveal that at high flow rates (Er ≈ 1000), individual CNC particles align with the flow exhibiting a weak chiral structure. In contrast, at lower flow rates (Er ≈ 241), they display the double-twisted cylinder structure. Understanding the flow effect on the alignment of the chiral liquid crystal can pave the way to designing 3D printed architectures with internal chirality for advanced mechanical and smart photonic applications.